Flame retarding compounds

ABSTRACT

Novel flame retarding compounds that comprise at least one sterically hindered nitroxyl, hydroxylamine or hydrocarbyloxyamine moiety and at least one conventional organohalogen or organophosphorus flame retardant moiety, represented by 
                 
         where   HA is independently of each other a sterically hindered nitroxyl, sterically hindered hydroxylamine or sterically hindered hydrocarbyloxyamine moiety,   L is independently of each other a direct bond or chemical linking group,   FRM is independently of each other an organohalogen or an organophosphorus flame reatardant moiety, and   x, y and z are each independently greater than or equal to 1,
 
are especially effective towards providing flame retardancy to organic polymer substrates.

This application claims the benefit under 35 USC 119(e) of U.S.provisional application Nos. 60/342,331, filed Dec. 21, 2001 and60/416,556, filed Oct. 7, 2002.

The instant invention pertains to novel flame retarding compounds thatcomprise at least one sterically hindered nitroxyl, hydroxylamine,hydrocarbyloxyamine moiety and at least one conventional organohalogenor organophosphorus flame retardant moiety.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 5,096,950 discloses the co-use of certain NOR (N-alkoxy)hindered amines with a brominated Sb₂O₃-containing flame retardant inpolypropylene.

U.S. Pat. No. 5,393,812 discloses polyolefin compositions which are madeflame retardant by a combination of a halogenated hydrocarbyl phosphateor phosphonate ester flame retardant in combination with a alkoxyaminefunctional hindered amine.

U.S. Pat. No. 5,844,026 discloses polyolefin compositions comprisingcertain NOR hindered amines and certain conventional flame retardants.

U.S. Pat. No. 6,117,995 discloses that certain N-alkoxy hindered aminesmay be used as flame retardants for organic polymers.

U.S. Pat. No. 6,271,377 discloses polyolefin compositions that compriseN-hydroxyalkoxy hindered amines and a halogenated flame retardant.

U.S. Pat. No. 6,309,987 and equivalent WO 99/54530 teach polyolefinnon-woven flame retardant fabrics that comprise N-alkoxyamines.

A Revolutionary UV Stable Flame Retardant System for Polyolefins—R.Srinivasan, A. Gupta and D. Horsey, Int. Conf. Addit. Polyolefins 1998,69-83, teaches polyolefins comprising certain NOR hindered amines withhalogen and phosphorus containing conventional flame retardants.

Advances in a Revolutionary Flame Retardant System for Polyolefins—R.Srinivasan, B. Rotzinger, Polyolefins 2000, Int. Conf Polyolefins 2000,571-581, teaches polyolefins comprising certain NOR hindered amines withbrominated and phosphorus containing flame retardants.

N. Kaprinidis and R. King, in an abstract posted on the Society ofPlastics Engineers website, posted September 2001, discuss the use ofNOR hindered amines as flame retardants in polyolefins. The abstract isfor a paper submitted to the Polymer Modifiers and Additives Divisionsubsection to be presented at the Polyolefins 2002 conference inHouston, Tex., Feb. 24, 2002. The website is www.PMAD.org.

EP 0792911 A2, discloses polyolefin compositions that comprisealkoxyamine functional hindered amines and tris(trihalogenopentyl)phosphate flame retardants.

WO 99/00450, copending U.S. application Nos. 09/502,239, filed Nov. 3,1999, and 09/714,717, filed Nov. 16, 2000, disclose the use of certainN-alkoxy hindered amines as flame retardants.

EP 1104766 discloses cross-linked phenoxyphosphazene compounds as flameretardants for synthetic resins.

The flame retardant (FR) market today is comprised of products whichfunction to interfere with the combustion process by chemical and/orphysical means. Mechanistically these FRs have been proposed to functionduring combustion of an article in either the gas phase, the condensedphase or both. The organohalogens are proposed to generate halogenspecies (e.g. HX) which interferes in the gas phase with free radicalorganic “fuel” from the polymer substrate. Synergists are proposed toreact with HX to form additional chemical species which interfere withcombustion in the gas phase, such as reaction of antimony oxide with HXto form antimony halide and water vapor. Antimony compounds such asantimony trioxide also act as radical scavengers forming antimonyhalides. Thus, they can inhibit the propagation of the fire.

Although antimony compounds are efficient in terms of cost performance,they recently raised concern because of the toxicity of the byproductswhich are formed during combustion in the presence of a halogenatedflame retardant. Antimony oxides often contain trace amounts of arseniccompounds which are suspected carcinogens. Because of these ecologicalconcerns, there is a movement to replace antimony trioxide in thepresent commercial flame retardant applications. However, it is verydifficult to find an effective synergist which is both environmentallyfriendly and efficient as far as cost performance is concerned.

Another reason to add flame retardant additives is to prevent drippingduring the application of the fire. During combustion, parts of thepolymer separate from the matrix in the shape of droplets. Often, thedroplets are flaming and impose tremendous danger for fire spread. It iscommon to add fillers such as talc in large amounts to the polymer, withnegative consequences on the mechanical properties. Other fillerssometimes used include calcium carbonate, magnesium carbonate, zincborate, silicates, silicones, glass fibres, glass bulbs, asbestos,kaolin, mica, barium sulfate, calcium sulfate, metal oxides, hydratesand hydroxides such as zinc oxide, magnesium hydroxide, aluminatrihydrate, silica, calcium silicate, magnesium silicate.

It has been found that polymers with good flame retardant properties areprepared when novel compounds are added that comprise at least onesterically hindered nitroxyl, hydroxylamine or hydrocarbyloxyaminemoiety and at least one conventional organohalogen or organophosphorusflame retardant moiety. With the use of these novel compounds, antimonycompounds and fillers may be largely reduced or replaced. As the instantcompounds are active as stabilizers, the polymer compositions of theinvention are efficiently protected from the deleterious effects oflight, oxygen and/or heat.

DETAILED DISCLOSURE

The instant invention pertains to novel flame retardant compounds thatcomprise at least one sterically hindered nitroxyl, hydroxylamine orhydrocarbyloxyamine moiety and at least one conventional organohalogenor organophosphorus flame retardant moiety.

The present compounds are of the formula

where

HA is independently of each other a sterically hindered nitroxyl,sterically hindered hydroxylamine or sterically hinderedhydrocarbyloxyamine moiety,

L is independently of each other a direct bond or chemical linkinggroup,

FRM is independently of each other an organohalogen or anorganophosphorus flame reatardant moiety, and

x, y and z are each independently greater than or equal to 1.

The present compounds that comprise at least one sterically hinderednitroxyl, hydroxylamine or hydrocarbyloxyamine moiety and at least oneconventional organohalogen or organophosphorus flame retardant moietyare for example represented by formula I

and the present compounds that comprise at least one sterically hinderedhydrocarbyloxyamine moiety and at least one conventional organohalogenor oganophosphorus moiety are further represented for example byformulae II and III

where in formulae I, II and III

R is hydrogen or methyl,

G₁ and G₂ are independently alkyl of 1 to 4 carbon atoms or are togetherpentamethylene,

x, y and z are each independently greater than or equal to 1,

L is independently of each other a direct bond or a chemical linkinggroup,

Z₁ and Z₂ are independently hydrogen or hydrocarbyl, or together form ahydrocarbylene group, or are independently —OR₁, —OCOR₁, —COOR₁,—CONR₁R₂, —NR₁COR₂, —COR₁ or —NR₁R₂,

R₁ and R₂ are independently of each other hydrogen or hydrocarbyl, or R₁and R₂ together form a hydrocarbylene group,

E is oxyl, hydroxyl, alkoxy, cycloalkoxy, aralkoxy, aryloxy, —O—CO—OG,—O—Si(G)₃, or —O—CH₂—OG where G is selected from the group consisting ofhydrogen, an aliphatic, araliphatic and aromatic moiety; or E is—O—T—(OH)_(b),

T is a straight or branched chain alkylene of 1 to 18 carbon atoms,cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of 5 to 18 carbonatoms, a straight or branched chain alkylene of 1 to 4 carbon atomssubstituted by phenyl or by phenyl substituted by one or two alkylgroups of 1 to 4 carbon atoms,

b is 1, 2 or 3 with the proviso that b cannot exceed the number ofcarbon atoms in T, and when b is 2 or 3, each hydroxyl group is attachedto a different carbon atoms of T, and

FRM is independently of each other an organohalogen or anorganophosphorus flame retardant moiety.

E is for example oxyl, hydroxyl, alkoxy, cycloalkoxy or aralkoxy. Forinstance, E is methoxy, propoxy, cyclohexyloxy or octyloxy.

The terms x, y and z independently may be for example 1 to about 200, 1to about 100, 1 to about 50, for instance 1 to about 25, 1 to about 10or 1 to about 5, for example, each may be independently 1, 2, 3, 4 or 5.

The term “hydrocarbyl group” broadly refers to a monovalent hydrocarbongroup in which the valency is derived by abstraction of a hydrogen froma carbon atom. Hydrocarbyl includes for example aliphatics (straight andbranched chain), cycloaliphatics, aromatics and mixed groups such asaralkyl, alkylaryl, alkynyl, cycloalkynyl. Hydrocarbyl includes suchgroups as alkyl, cycloalkyl, aryl, aralkyl, alkylaryl, alkenyl, andcycloalkenyl. A hydrocarbyl may optionally be interrupted by carbonyl,carboxyl, amino, amido, thio, sulfoxide, sulfonyl and ether groupsand/or may optionally be substituted by hydroxy, amino, amido, carboxyland thio groups.

The term “hydrocarbylene” broadly refers to any divalent hydrocarbon inwhich both valencies derive by abstraction of hydrogens from carbonatoms. Included within the definition of hydrocarbylene are the samegroups as indicated herein for hydrocarbyl, with of course, the extravalency, for example alkylene, alkenylene, arylene, alkylaryl, etc.

For the purposes of this invention, and as is understood in the art, theterm “moiety” means a chemical functional group when it is part of alarger compound, for example when part of a compound of formula I, II orIII. For example, the term “organohalogen or organophosphorus flameretardant moiety” refers to the conventional organic flame retardantportion(s) of the compounds of formulae I, II and III. Likewise the term“hindered hydrocarbyloxyamine moiety” refers to the portion of formulaeI, II and III with hydrocarbyloxyamine additive functionality. For thepurposes of this invention, the term moiety is not limited to a singleactive functionality. For example, a chemical group containing two (ormore) hindered amine groups may be considered a single moiety.

Alkyl is a straight or branched chain of for example 1 to 24 carbonatoms, for instance, 1 to 18 carbon atoms or 1 to 12 carbon atoms, andis for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl,n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Cycloalkyl groups are for example of from 5 to 7 carbon atoms andinclude cyclopentyl and cyclohexyl; typical cycloalkenyl groups includecyclohexenyl.

Aralkyl groups are for example of 7 to 9 carbon atoms and includebenzyl, alpha-methyl-benzyl, alpha,alpha-dimethylbenzyl or phenethyl.

Aryl is for instance phenyl, napthyl and biphenyl.

Alkoxy and aryloxy groups are defined as for the present alkyl and arylgroups.

Halogen is for instance chloro and bromo.

The compounds of the present invention do not have any peroxy linkages.Likewise, the only possible N—O bond is in the HA moieties (in which itis necessary).

Chemical Linking Groups L

The chemical linking groups L may for example be any divalent orpolyvalent linking group. Linking groups L are for example esters,amides, and other common divalent or polyvalent groups, for example—OCO—, —COO—, —O—, —CONR₁—, —NR₁CO—, —CO—, —NR₁—, —S—₁, —SO—, SO₂—,—CSO—, —COS—, —CSS—, triazinyl, and the like.

R₁ is independently of each other hydrogen or a hydrocarbyl group.

Polyvalent is for example trivalent and tetravalent or greater.Triazinyl is a trivalent linking group.

Linking groups L may be a divalent hydrocarbylene group or polyvalentgroup that comprises one or more of the above ester, amide, etc.,groups. The linking groups L may be terminated, interrupted orsubstituted by said groups.

The linking groups L may be a polymeric backbone, for example apolyamine, a polyglycol, a polyester or a polyamine/polytriazine polymeror oligomer. In this instance L is polyvalent.

A polymeric backbone (polyvalent backbone) defined herein may be forexample any polymeric or oligomeric backbone known in the art as part ofpolymeric or oligomeric polymer additives. For exampletriazine-containing polymeric backbones that are part of commercialhindered amine compounds, for example Chimassorb® 944, CAS #71878-19-8.Other suitable polyvalent backbones that may define the linking group Lare as in the commercial products:

where R′=R″ or H

and where R″=

The polymeric backbone linking groups of the present invention may bederived from known polymerization methods, for example condensationpolymerization or free radical polymerization of ethylenicallyunsaturated monomers. Certain of known organohalogen andorganophosphorus flame retardants comprise ethylenically unsaturatedgroups which may be co-polymerized with present sterically hinderednitroxyl, hydroxylamine and hydrocarbyloxyamine compounds that likewisecomprise ethylenically unsaturated groups.

Examples of flame retardant moieties that comprise ethylenicallyunsaturated groups are for example

Examples of flame retardant moieties suitable for condensationpolymerization, as a method of bonding one or more of them to a presentsterically hindered nitroxyl, hydroxylamine or hydrocarbyloxyaminemoiety, are for example

Other suitable polyvalent backbones are as in the compounds:

where R′ is

Tinuvin® and Chimassorb® are protected trade names of Ciba SpecialtyChemicals Corp. Sanduvor® and Hostavin® are protected trade names ofClariant. Cyasorb® is a protected trade name of Cytec Corporation.Uvinul® is a protected trade name of BASF. Uvasil® is a protected tradename of Enichem. Uvasorb® is a protected trade name of 3V Sigma.

Organohalogen and Organophosphorus Flame Retardant Moieties (FRM)

The present FRM moieties are for example a hydrocarbyl group substitutedby multiple halogen atoms, for example alkyl of 1 to 18 carbon atomssubstituted by 1 to 37 bromine or chlorine atoms, cycloalkyl of 5 to 12carbon atoms substituted by 1 to 23 bromine or chlorine atoms, aralkylof 7 to 15 carbon atoms substituted by 1 to 5 bromine or chlorine atoms,or aryl of 6 to 12 carbon atoms substituted by 5 to 9 bromine orchlorine atoms.

For example the FRM moieties are hydrocarbyl groups substituted by 3, 4,5, 6, 7, or 8 chlorine or bromine atoms.

The present FRM moieties are for example:

wherein T₁ and T₂ are independently alkyl, aryl, alkoxy, aralkoxy ordialkylamino; or said alkyl, aryl, alkoxy, aralkoxy or dialkylaminosubstituted by 1 to 8 halogen atoms, R₁ is defined as above;

where X is chlorine or bromine;

where one of the open bonds may be bonded to T₁, defined above,

where one of the open bonds may be bonded to T₁, defined above,

where one to three of the open bonds may be bonded to T₁, defined above,

where one to three of the open bonds may be bonded to T₁, defined above,

where one to three of the open bonds may be bonded to T₁, defined above,

where one of the open bonds may be bound to alkyl or aryl; or said alkylor aryl substituted by 1 to 8 halogen atoms,

where one of the open bonds may be bound to alkyl or aryl; or said alkylor aryl substituted by 1 to 8 halogen atoms,

where X is chlorine or bromine; and where one of the open bonds may bebonded to T₁, defined above,

or

-   -   —(phosphazene flame retardant)

The phosphazene flame retardants of component are well known in the art.They are disclosed for example in EP1104766, JP07292233, DE19828541,DE1988536, JP11263885, U.S. Pat. Nos. 4,107,108, 4,108,805 and 4,079,035and 6,265,599. The relevant disclosures of the U.S. Patents are herebyincorporated by reference.

The FRM moieties are for example based on well known commercialorganohalogen, organophosphorus and melamine based flame retardants. Theterm “based on” means potentially derived directly from or having thesame active structure less the requisite number of valencies.

Oganohalogen flame retardants are for example:

Chloroalkyl phosphate esters (ANTIBLAZE® AB-100, Albright & Wilson;FYROL® FR-2, Akzo Nobel),

polybrominated diphenyl oxide (DE-60F, Great Lakes Corp.),

decabromodiphenyl oxide (DBDPO; SAYTEX® 102E),

tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate (PB 370®, FMC Corp.),

bis(2,3-dibromopropyl ether) of bisphenol A (PE68),

brominated epoxy resin,

ethylene-bis(tetrabromophthalimide) (SAYTEX® BT-93),

bis(hexachlorocyclopentadieno)cyclooctane (DECLORANE PLUS®),

chlorinated paraffins,

1,2-bis(tribromophenoxy)ethane (FF680),

tetrabromo-bisphenol A (SAYTEX® RB100),

ethylene bis-(dibromo-norbornanedicarboximide) (SAYTEX®BN-451),

bis-(hexachlorocyclopentadieno) cyclooctane,

tris-(2,3-dibromopropyl)-isocyanurate, and

ethylene-bis-tetrabromophthalimide.

The organophophorus flame retardants are for example:

Tetraphenyl resorcinol diphosphite (FYROLFLEX® RDP, Akzo Nobel),

triphenyl phosphate,

ammonium polyphosphate (APP) or (HOSTAFLAM® AP750),

resorcinol diphosphate oligomer (RDP),

phosphazene flame retardants and

ethylenediamine diphosphate (EDAP).

Melamine based flame retardants are for example:

melamine cyanurate, MELAPUR® MC,

melamine borate,

melamine phosphate, MELAPUR® P 46,

melamine polyphosphate MELAPUR® 200 and

melamine pyrophosphate.

The halogenated flame retardants useful in the present invention may beselected from organic aromatic halogenated compounds such as halogenatedbenzenes, biphenyls, phenols, ethers or esters thereof, bisphenols,diphenyloxides, aromatic carboxylic acids or polyacids, anhydrides,amides or imides thereof; organic cycloaliphatic or polycycloaliphatichalogenated compounds; and organic aliphatic halogenated compounds suchas halogenated paraffins, oligo- or polymers, alkylphosphates oralkylisocyanurates. These components are largely known in the art, seee.g. U.S. Pat. Nos. 4,579,906 (e.g. col. 3, lines 30-41), 5,393,812; seealso Plastics Additives Handbook, Ed. by H. Zweifel, 5^(th) Ed., HanserPubl., Munich 2001, pp. 681-698.

Sterically Hindered Nitroxyl, Hydroxylamine and HydrocarbyloxyamineMoieties (HA)

The HA moieties are for example based on well known commercial hinderednitroxyl, hydroxylamine and hydrocarbyloxyamine stabilizers. The term“based on” means potentially derived directly from or having the sameactive structure less the requisite number of valencies.

Hindered hydrocarbyloxyamine stabilizers are well known in the art, alsoknown as N-alkoxy hindered amines and NOR hindered amines or NORhindered amine light stabilizers or NOR HALS.

They are disclosed for example in U.S. Pat. Nos. 5,004,770, 5,204,473,5,096,950, 5,300,544, 5,112,890, 5,124,378, 5,145,893, 5,216,156,5,844,026, 6,117,995, 6,271,377, and U.S. application Ser. Nos.09/505,529, filed Feb. 17, 2000, 09/794,710, filed Feb. 27, 2001,09/714,717, filed Nov. 16, 2000, 09/502,239, filed Nov. 3, 1999 and60/312,517, filed Aug. 15, 2001. The relevant disclosures of thesepatents and applications are hereby incorporated by reference.

U.S. Pat. No. 6,271,377, and U.S. application Ser. Nos. 09/505,529,filed Feb. 17, 2000, and 09/794,710, filed Feb. 27, 2001, cited abovedisclose hindered hydroxyalkoxyamine stabilizers. For the purposes ofthis invention, the hindered hydroxyalkoxyamine stabilizers areconsidered a subset of the hindered hydrocarbyloxyamine stabilizers.Hindered hydroxyalkoxyamine stabilizers are also known asN-hydroxyalkoxy hindered amines, or NORol HALS.

Typical hindered nitroxyls includebis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine,4-ethoxy-1-oxyl-2,2,6,6-tetramethylpiperidine,4-propoxy-1-oxyl-2,2,6,6-tetramethylpiperidine,4-acetamido-1-oxyl-2,2,6,6-tetramethylpiperidine,1-oxyl-2,2,6,6-tetramethylpiperidine,1-oxyl-2,2,6,6-tetramethylpiperidin-4-one,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 2-ethylhexanoate,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate,1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 4-t-butyl-benzoate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) succinate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) n-butylmalonate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate,bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate,N,N′-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipamide,N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)caprolactam,N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) dodecylsuccinimide,2,4,6-tris-[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)]-s-triazine,4,4′-ethylenebis(1-oxyl-2,2,6,6-tetramethylpiperazin-3-one),2-oxyl-1,1,3,3-tetramethyl-2-isobenzazole,1-oxyl-2,2,5,5-tetramethylpyrrolidine, andN,N-bis-(1,1,3,3-tetramethylbutyl)nitroxide.

Nitroxyl stabilizers are for examplebis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine,4-ethoxy-1-oxyl-2,2,6,6-tetramethylpiperidine,4-propoxy-1-oxyl-2,2,6,6-tetramethylpiperidine,4-acetamido-1-oxyl-2,2,6,6-tetramethylpiperidine,1-oxyl-2,2,6,6-tetramethylpiperidine, and1-oxyl-2,2,6,6-tetramethylpiperidin-4-one.

A specific embodiment is where the nitroxyl stabilizers arebis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine.

Hydroxylamine stabilizers are for example those disclosed in U.S. Pat.Nos. 4,590,231, 4,668,721, 4,691,015, 4,831,134, 5,006,577, and5,064,883, the relevant parts of which are incorporated herein byreference.

Specific examples of suitable compounds that the present HA moieties maybe based on include:

(a) the reaction product of2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazinewith N,N′-bis(3-aminopropyl)ethylenediamine) [CAS Reg. No. 191680-81-6];

(b) 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine;

(c) bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;

(d)2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxy-ethylamino-s-triazine;

(e) bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate;

(h)2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-choro-s-triazine;

(i)1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine;

(j) 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine;

(k)1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;

(l) bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;

(m) bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)adipate;

(n)2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butyl-amino}-6-(2-hydroxyethylamino)-s-triazine;and

(o) the compound of formula

in which n is from 1 to 15.

Compound (o) is disclosed in example 2 of U.S. Pat. No. 6,117,995.

It is apparent to those skilled in the art that there is potentiallysignificant overlap between the definition of the HA moieties and thelinking groups L. That is, these groups are not mutually exclusive; inone compound the HA moiety and the L groups may be defined in more thanone way and still correctly be described by formula I, II and III.

The sterically hindered nitroxyl, hydroxylamine or hydrocarbyloxyaminemoiety is for example selected from the group consisting of

and the corresponding nitroxyl and hydroxylamine moieties whereappropriate.

The present novel flame retardant compounds are advantageously employedin organic polymer substrates. As the instant nitroxyl, hydroxylamineand hydrocarbyloxyamine compounds are active as stabilizers, the polymercompositions of the invention are efficiently protected from thedeleterious effects of light, oxygen and/or heat, as well as beingimparted with flame retardancy.

Accordingly, the present invention also pertains to a flame retardantcomposition which comprises

-   -   (A) an organic polymer substrate and    -   (B) an effective flame retarding amount of at least one compound        of the formula

Advantageously, the compositions of the invention may further contain aconventional flame retardant not bound to a hindered amine moiety, forexample at least one compound selected from the group consisting of theorganohalogen and the organophosphorus flame retardants. Theconventional flame retardants are as described above.

Components A and B and optional further components may comprise one or amixture of more than one chemical species.

Advantageously, present composition contains only minor amounts ofantimony compounds such as Sb₂O₃, e.g. less than about 1%, for instanceless than about 0.1% by weight of the polymer component A; for example,the present compositions are essentially free of antimony.

Flame-retardant fillers are not required in order to improve the flameretardant properties and achieve a higher rating, e.g. in the UL-94burning test (infra). Consequently, the compositions of the presentinvention may contain only minor amounts of flame-retardant fillers,e.g. less than about 3%, for instance less than about 1%, for exampleless than about 0.1% by weight of the polymer component A; for example,the present compositions are essentially free of flame-retardantfillers.

Flame-retardant fillers are known in the art and are selected from thegroup consisting of magnesium hydroxide, alumina trihydrate and zincborate. Flame-retardant fillers are inorganic compounds employed forflame-retardant properties, and at high enough levels to be considered“filler”.

If conventional fillers such as talc, calcium carbonate and the like arenormally employed for instance for flow properties in order to reducethe spread of flaming droplets (not flame-retardant per se), suchconventional fillers may also be reduced with the use of the presentcompositions. For instance, the present compositions may contain onlyminor amounts of conventional fillers, for example less than about 3%,for instance less than 1%, for example less than about 0.1% by weight ofthe polymer component A; for example, the present compositions areessentially free of conventional fillers.

Further, the present invention allows for conventional fillers to takethe place of more expensive flame-retardant fillers.

The polymeric substrate of component A is any of a wide variety ofpolymeric types including polyolefins, polystyrenics, and PVC. Forexample, the polymer substrate may be selected from the group of resinsconsisting of the polyolefins, the thermoplastic olefins, styrenicpolymers and copolymers, ABS and polymers which contain hetero atoms,double bonds or aromatic rings. Specific embodiments are where componentA is polypropylene, polyethylene, thermoplastic olefin (TPO), ABS orhigh impact polystyrene.

For example, the polymer substrate is selected from the group of resinsconsisting of the polyolefins, the thermoplastic olefins, styrenicpolymers and copolymers, and ABS.

Another embodiment of the present invention is where the polymersubstrate is selected from the group consisting of polypropylene,polyethylene, thermoplastic olefin (TPO), ABS and high impactpolystyrene.

For instance, the polymer substrate is polypropylene, polyethylene orthermoplastic olefin (TPO). Organic polymers of component A are forexample thermoplastic polymers such as polyolefins like polyethylene,polypropylene or copolymers thereof. The thermoplastic polymer is forexample polypropylene.

Further examples for organic polymers (component A) are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE).Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, for example polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π- or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).        2. Mixtures of the polymers mentioned under 1), for example        mixtures of polypropylene with polyisobutylene, polypropylene        with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of        different types of polyethylene (for example LDPE/HDPE).        3. Copolymers of monoolefins and diolefins with each other or        with other vinyl monomers, for example ethylene/propylene        copolymers, linear low density polyethylene (LLDPE) and mixtures        thereof with low density polyethylene (LDPE),        propylene/but-1-ene copolymers, propylene/isobutylene        copolymers, ethylene/but-1-ene copolymers, ethylene/hexene        copolymers, ethylene/methylpentene copolymers, ethylene/heptene        copolymers, ethylene/octene copolymers,        ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin        copolymers (e.g. ethylene/norbornene like COC),        ethylene/1-olefins copolymers, where the 1-olefin is generated        in-situ; propylene/butadiene copolymers, isobutylene/isoprene        copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl        acrylate copolymers, ethylene/alkyl methacrylate copolymers,        ethylene/vinyl acetate copolymers or ethylene/acrylic acid        copolymers and their salts (ionomers) as well as terpolymers of        ethylene with propylene and a diene such as hexadiene,        dicyclopentadiene or ethylidene-norbornene; and mixtures of such        copolymers with one another and with polymers mentioned in 1)        above, for example polypropylene/ethylene-propylene copolymers,        LDPE/ethylene-vinyl acetate copolymers (EVA),        LDPE/ethylene-acrylic acid copolymers (EM), LLDPE/EVA, LLDPE/EAA        and alternating or random polyal-kylene/carbon monoxide        copolymers and mixtures thereof with other polymers, for example        polyamides.        4. Hydrocarbon resins (for example C₅-C₉) including hydrogenated        modifications thereof (e.g. tackifiers) and mixtures of        polyalkylenes and starch.        Homopolymers and copolymers from 1.)-4.) may have any        stereostructure including syndiotactic, isotactic,        hemi-isotactic or atactic; for example atactic polymers.        Stereoblock polymers are also included.        5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).        6. Aromatic homopolymers and copolymers derived from vinyl        aromatic monomers including styrene, α-methylstyrene, all        isomers of vinyl toluene, especially p-vinyltoluene, all isomers        of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl        naphthalene, and vinyl anthracene, and mixtures thereof.        Homopolymers and copolymers may have any stereostructure        including syndiotactic, isotactic, hemi-isotactic or atactic;        for example atactic polymers. Stereoblock polymers are also        included.        6a. Copolymers including aforementioned vinyl aromatic monomers        and comonomers selected from ethylene, propylene, dienes,        nitriles, acids, maleic anhydrides, maleimides, vinyl acetate        and vinyl chloride or acrylic derivatives and mixtures thereof,        for example styrene/butadiene, styrene/acrylonitrile,        styrene/ethylene (interpolymers), styrene/alkyl methacrylate,        styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl        methacrylate, styrene/maleic anhydride,        styrene/acrylonitrile/methyl acrylate; mixtures of high impact        strength of styrene copolymers and another polymer, for example        a polyacrylate, a diene polymer or an ethylene/propylene/diene        terpolymer; and block copolymers of styrene such as        styrene/butadiene/styrene, styrene/isoprene/styrene,        styrene/ethylene/butylene/styrene or        styrene/ethylene/propylene/styrene.        6b. Hydrogenated aromatic polymers derived from hydrogenation of        polymers mentioned under 6.), especially including        polycyclohexylethylene (PCHE) prepared by hydrogenating atactic        polystyrene, often referred to as polyvinylcyclohexane (PVCH).        6c. Hydrogenated aromatic polymers derived from hydrogenation of        polymers mentioned under 6a.).        Homopolymers and copolymers may have any stereostructure        including syndiotactic, isotactic, hemi-isotactic or atactic;        for example atactic polymers. Stereoblock polymers are also        included.        7. Graft copolymers of vinyl aromatic monomers such as styrene        or α-methylstyrene, for example styrene on polybutadiene,        styrene on polybutadiene-styrene or polybutadiene-acrylonitrile        copolymers; styrene and acrylonitrile (or methacrylonitrile) on        polybutadiene; styrene, acrylonitrile and methyl methacrylate on        polybutadiene; styrene and maleic anhydride on polybutadiene;        styrene, acrylonitrile and maleic anhydride or maleimide on        polybutadiene; styrene and maleimide on polybutadiene; styrene        and alkyl acrylates or methacrylates on polybutadiene; styrene        and acrylonitrile on ethylene/propylene/diene terpolymers;        styrene and acrylonitrile on polyalkyl acrylates or polyalkyl        methacrylates, styrene and acrylonitrile on acrylate/butadiene        copolymers, as well as mixtures thereof with the copolymers        listed under 6), for example the copolymer mixtures known as        ABS, MBS, ASA or AES polymers.        8. Halogen-containing polymers such as polychloroprene,        chlorinated rubbers, chlorinated and brominated copolymer of        isobutylene-isoprene (halobutyl rubber), chlorinated or        sulfochlorinated polyethylene, copolymers of ethylene and        chlorinated ethylene, epichlorohydrin homo- and copolymers,        especially polymers of halogen-containing vinyl compounds, for        example polyvinyl chloride, polyvinylidene chloride, polyvinyl        fluoride, polyvinylidene fluoride, as well as copolymers thereof        such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl        acetate or vinylidene chloride/vinyl acetate copolymers.        9. Polymers derived from α,β-unsaturated acids and derivatives        thereof such as polyacrylates and polymethacrylates; polymethyl        methacrylates, polyacrylamides and polyacrylonitriles,        impact-modified with butyl acrylate.        10. Copolymers of the monomers mentioned under 9) with each        other or with other unsaturated monomers, for example        acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate        copolymers, acrylonitrile/alkoxyalkyl acrylate or        acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl        methacrylate/butadiene terpolymers.        11. Polymers derived from unsaturated alcohols and amines or the        acyl derivatives or acetals thereof, for example polyvinyl        alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl        benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl        phthalate or polyallyl melamine; as well as their copolymers        with olefins mentioned in 1) above.        12. Homopolymers and copolymers of cyclic ethers such as        polyalkylene glycols, polyethylene oxide, polypropylene oxide or        copolymers thereof with bisglycidyl ethers.        13. Polyacetals such as polyoxymethylene and those        polyoxymethylenes which contain ethylene oxide as a comonomer;        polyacetals modified with thermoplastic polyurethanes, acrylates        or MBS.        14. Polyphenylene oxides and sulfides, and mixtures of        polyphenylene oxides with styrene polymers or polyamides.        15. Polyurethanes derived from hydroxyl-terminated polyethers,        polyesters or polybutadienes on the one hand and aliphatic or        aromatic polyisocyanates on the other, as well as precursors        thereof.        16. Polyamides and copolyamides derived from diamines and        dicarboxylic acids and/or from aminocarboxylic acids or the        corresponding lactams, for example polyamide 4, polyamide 6,        polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11,        polyamide 12, aromatic polyamides starting from m-xylene diamine        and adipic acid; polyamides prepared from hexamethylenediamine        and isophthalic or/and terephthalic acid and with or without an        elastomer as modifier, for example        poly-2,4,4,-trimethylhexamethylene terephthalamide or        poly-m-phenylene isophthalamide; and also block copolymers of        the aforementioned polyamides with polyolefins, olefin        copolymers, ionomers or chemically bonded or grafted elastomers;        or with polyethers, e.g. with polyethylene glycol, polypropylene        glycol or polytetramethylene glycol; as well as polyamides or        copolyamides modified with EPDM or ABS; and polyamides condensed        during processing (RIM polyamide systems).        17. Polyureas, polyimides, polyamide-imides, polyetherimids,        polyesterimids, polyhydantoins and polybenzimidazoles.        18. Polyesters derived from dicarboxylic acids and diols and/or        from hydroxycarboxylic acids or the corresponding lactones, for        example polyethylene terephthalate, polybutylene terephthalate,        poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene        naphthalate (PAN) and polyhydroxybenzoates, as well as block        copolyether esters derived from hydroxyl-terminated polyethers;        and also polyesters modified with polycarbonates or MBS.        19. Polycarbonates and polyester carbonates.        20. Polyketones.        21. Polysulfones, polyether sulfones and polyether ketones.        22. Blends of the aforementioned polymers (polyblends), for        example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS,        PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE,        PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR,        POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers,        PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

Component B is advantageously contained in the compositions of theinvention in an amount from about 0.01 to about 20% by weight based onthe polymeric substrate A; for example about 0.1 to about 10%, forexample from about 0.25 to about 8% by weight; for instance from about0.5 to about 3% by weight. For example about 0.05, 1, 1.5, 2, 3, 4 or 5weight percent.

If a further conventional flame retardant is present in the compositionsof this invention, it is advantageously contained in an amount fromabout 0.5 to about 45% by weight of the polymeric substrate A; forinstance about 3 to about 40%; for example about 5 to about 35% byweight of component A.

The ratio (parts by weight) of the compounds of this invention tofurther conventional flame retardants is for example between about 1:5to about 1:200, for instance from about 1:50 to about 1:100, or about1:10 to about 1:25. For example the ratio of component B to furtherconventional flame retardants is from about 1:10 to about 1:200, fromabout 1:25 to about 1:200, from about 1:50 to about 1:200 or from about1:100 to about 1:200. For example, the weight ratio of component B tofurther conventional flame retardants is from about 1:5 to about 1:100,from about 1:5 to about 1:50, from about 1:5 to about 1:25, or fromabout 1:5 to about 1:10.

The amount of the further conventional flame retardants employed alsodepends on the effectiveness of the specific compound(s), the polymerand the specific application type; for example, an amount of 5 to 15% byweight of the compound tris[3-bromo-2,2-bis(bromomethyl)propyl]phosphate may be as efficient as an amount of 30 to 45% by weight of thecompound decabromodiphenyl oxide in respect of the flame retardancy ofthe final composition.

The resulting stabilized compositions of the invention may optionallyalso contain various conventional additives, for example in amounts fromabout 0.01 to about 10%, for instance from about 0.025 to about 4%, forexample from about 0.1 to about 2% by weight of component A, such as thematerials listed below, or mixtures thereof.

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec 1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.1.7. O—, N— and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso-cyanurate.1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis-(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1 supplied by Uniroyal).1.18. Ascorbic acid (vitamin C)1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine; for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octa-decanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- und dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.2. UV absorbers and light stabilisers2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl- 2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole, 2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxy-phenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂

₂— where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)-phenyl]-benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)-phenyl]benzotriazole.2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyidithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensateof2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane und epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5, 5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.Specific examples are the following phosphites:Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba-Geigy),tris(nonylphenyl) phosphite,

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.7. Thiosynergists, for example, dilauryl thiodipropionate or distearylthiodipropionate.8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zincdibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.9. Polyamide stabilisers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zinkpyrocatecholate.11. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, for example, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers (ionomers). Specific examples are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene) sorbitol, und1,3:2,4-di(benzylidene)sorbitol.12. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.13. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.15. Amine oxides, for example amine oxide derivatives as disclosed inU.S. Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl amine oxide,tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amineoxide. U.S. Pat. Nos. 5,844,029 and 5,880,191 disclose the use ofsaturated hydrocarbon amine oxides towards the stabilization ofthermoplastic resins. It is disclosed that the thermoplasticcompositions may further contain a stabilizer or mixture of stabilizersselected from phenolic antioxidants, hindered amine light stabilizers,ultraviolet light absorbers, organic phosphorus compounds, alkalinemetal salts of fatty acids and thiosynergists.

The compositions may also contain a further conventional flameretardant, for instance one or more conventional organohalogen,organophosphorus or melamine based flame retardants. For example:

Oganohalogen flame retardants are for example:

-   -   Chloroalkyl phosphate esters (ANTIBLAZE® AB-100, Albright &        Wilson; FYROL® FR-2, Akzo Nobel),    -   polybrominated diphenyl oxide (DE-60F, Great Lakes Corp.),    -   decabromodiphenyl oxide (DBDPO; SAYTEX® 102E),    -   tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate (PB 370®, FMC        Corp.),    -   bis(2,3-dibromopropyl ether) of bisphenol A (PE68),    -   brominated epoxy resin,    -   ethylene-bis(tetrabromophthalimide) (SAYTEX® BT-93),    -   bis(hexachlorocyclopentadieno)cyclooctane (DECLORANE PLUS®),    -   chlorinated paraffins,    -   1,2-bis(tribromophenoxy)ethane (FF680),    -   tetrabromo-bisphenol A (SAYTEX® RB100),    -   ethylene bis-(dibromo-norbornanedicarboximide) (SAYTEX® BN-451),    -   bis-(hexachlorocyclopentadieno) cyclooctane,    -   tris-(2,3-dibromopropyl)-isocyanurate, and    -   ethylene-bis-tetrabromophthalimide.

The organophophorus flame retardants are for example:

-   -   Tetraphenyl resorcinol diphosphite (FYROLFLEX® RDP, Akzo Nobel),    -   triphenyl phosphate,    -   ammonium polyphosphate (APP) or (HOSTAFLAM® AP750),    -   resorcinol diphosphate oligomer (RDP),    -   phosphazene flame retardants and    -   ethylenediamine diphosphate (EDAP).

Melamine based flame retardants are for example:

-   -   melamine cyanurate, MELAPUR® MC,    -   melamine borate,    -   melamine phosphate, MELAPUR@ P 46,    -   melamine polyphosphate MELAPUR® 200 and    -   melamine pyrophosphate.

Specific examples of additives are phenolic antioxidants (item 1 of thelist), further sterically hindered amines (item 2.6 of the list), lightstabilizers of the benzotriazole and/or o-hydroxyphenyltriazine class(items 2.1 and 2.8 of the list), phosphites and phosphonites (item 4 ofthe list) and peroxide-destroying compounds (item 5.) of the list.

Additional specific examples of additives (stabilizers) which arebenzofuran-2-ones, such as described, for example, in U.S. Pat. No.4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312.

The instant composition can additionally contain another UV absorberselected from the group consisting of the s-triazines, the oxanilides,the hydroxybenzophenones, benzoates and the (α-cyanoacrylates.Particularly, the instant composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof. For example, additional componentsare selected from pigments, dyes, plasticizers, antioxidants,thixotropic agents, levelling assistants, basic costabilizers, furtherlight stabilizers like UV absorbers and/or sterically hindered amines,metal passivators, metal oxides, organophosphorus compounds,hydroxylamines, and mixtures thereof, especially pigments, phenolicantioxidants, calcium stearate, zinc stearate, UV absorbers of the2-(2′-hydroxyphenyl)benzotriazole and 2-(2-Hydroxyphenyl)-1,3,5-triazineclasses, and sterically hindered amines.

The additives of the invention and optional further components may beadded to the polymer material individually or mixed with one another. Ifdesired, the individual components can be mixed with one another beforeincorporation into the polymer for example by dry blending, compactionor in the melt.

Conveniently, the additives of this invention and possibly furtheradditives as described above may be dry blended and then extruded, forinstance in a twin screw extruder at 180-220° C., with or withoutnitrogen atmosphere. The material thus obtained may be further processedaccording to known methods. The surface of the articles formed do notshow any loss of gloss or any kind of roughness.

Further, the instant invention pertains to a process for imparting lightstability and flame retardancy to an organic polymeric substrate, whichprocess comprises adding to said polymeric substrate an effective flameretarding amount of at least one compound of formula

The incorporation of the additives of the invention and optional furthercomponents into the polymer is carried out by known methods such as dryblending in the form of a powder, or wet mixing in the form ofsolutions, dispersions or suspensions for example in an inert solvent,water or oil. The additives of the invention and optional furtheradditives may be incorporated, for example, before or after molding oralso by applying the dissolved or dispersed additve or additive mixtureto the polymer material, with or without subsequent evaporation of thesolvent or the suspension/dispersion agent. They may be added directlyinto the processing apparatus (e.g. extruders, internal mixers, etc),e.g. as a dry mixture or powder or as solution or dispersion orsuspension or melt.

The incorporation can be carried out in any heatable container equippedwith a stirrer, e.g. in a closed apparatus such as a kneader, mixer orstirred vessel. The incorporation is for example carried out in anextruder or in a kneader. It is immaterial whether processing takesplace in an inert atmosphere or in the presence of oxygen.

The addition of the additive or additive blend to the polymer can becarried out in all customary mixing machines in which the polymer ismelted and mixed with the additives. Suitable machines are known tothose skilled in the art. They are predominantly mixers, kneaders andextruders.

The process is for instance carried out in an extruder by introducingthe additive during processing.

Specific examples of suitable processing machines are single-screwextruders, contrarotating and corotating twin-screw extruders,planetary-gear extruders, ring extruders or cokneaders. It is alsopossible to use processing machines provided with at least one gasremoval compartment to which a vacuum can be applied.

Suitable extruders and kneaders are described, for example, in Handbuchder Kunststoffextrusion, Vol. 1 Grundlagen, Editors F. Hensen, W.Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol. 2Extrusionsanlagen 1986, ISBN 3-446-14329-7).

For example, the screw length is 1-60 screw diameters, for example 35-48screw diameters. The rotational speed of the screw is for instance10-600 rotations per minute (rpm), for example 25-300 rpm.

The maximum throughput is dependent on the screw diameter, therotational speed and the driving force. The process of the presentinvention can also be carried out at a level lower than maximumthroughput by varying the parameters mentioned or employing weighingmachines delivering dosage amounts.

If a plurality of components are added, these can be premixed or addedindividually.

The additives of the invention and optional further additives can alsobe sprayed onto the polymer material. They are able to dilute otheradditives (for example the conventional additives indicated above) ortheir melts so that they can be sprayed also together with theseadditives onto the material. Addition by spraying during thedeactivation of the polymerization catalysts is particularlyadvantageous; in this case, the steam evolved may be used fordeactivation of the catalyst. In the case of spherically polymerizedpolyolefins it may, for example, be advantageous to apply the additivesof the invention, optionally together with other additives, by spraying.

The additives of the invention and optional further additives can alsobe added to the polymer in the form of a masterbatch (“concentrate”)which contains the components in a concentration of, for example, about1% to about 40%, for example about 2% to about 20% by weightincorporated in a polymer. The polymer must not be necessarily ofidentical structure than the polymer where the additives are addedfinally. In such operations, the polymer can be used in the form ofpowder, granules, solutions, suspensions or in the form of latices.

Incorporation can take place prior to or during the shaping operation.The materials containing the additives of the invention described hereinare for example used for the production of molded articles, for examplerotomolded articles, injection molded articles, profiles and the like.Thus,

a molded polymer article made flame retardant by the incorporation of atleast one compound of the formula

is another object of the invention.

It is also contemplated that PTFE, polytetrafluoroethylene (for exampleTeflone® 6C; E. I. Du Pont), may be advantageously added to the presentcompositions as an additional flame retardant, as disclosed in U.S.application Ser. No. 60/312,517, filed Aug. 15, 2001.

The effective flame retarding amount of component B is that needed toshow flame retarding efficacy as measured by one of the standard methodsused to assess flame retardancy. These include the NFPA 701 StandardMethods of Fire Tests for Flame-Resistant Textiles and Films, 1989 and1996 editions; the UL 94 Test for Flammability of Plastic Materials forParts in Devices and Appliances, 5th Edition, Oct. 29, 1996; LimitingOxygen Index (LOI), ASTM D-2863; and Cone Calorimetry, ASTM E-1354.Ratings according to the UL 94 V test are as compiled in the followingtable:

Afterflame Burning Burn to Rating time drips Clamp V-0 <10 s no no V-1<30 s no no V-2 <30 s yes no Fail <30 s yes Fail >30 s no

Coadditives found particularly useful for use with the instant compoundsin flame retardant compositions are as follows:

UV absorbers:

2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole, (TINUVIN® 234, CibaSpecialty Chemicals Corp.);

2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, (TINUVIN® P, CibaSpecialty Chemicals Corp.);

5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,(TINUVIN® 327, Ciba Specialty Chemicals Corp.);

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole, (TINUVIN® 328,Ciba Specialty Chemicals Corp.);

2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole, (TINUVIN®928, Ciba Specialty Chemicals Corp.);

2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, (TINUVIN®120, Ciba Specialty Chemicals Corp.);

2-hydroxy-4-n-octyloxybenzophenone, (CHIMASSORB® 81, Ciba SpecialtyChemicals Corp.);

2,4-bis(2,4-dimethyphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine,(CYASORB® 1164, Cytec).

The following examples are meant for illustrative purposes only and arenot to be construed to limit the scope of this invention in any mannerwhatsoever. Where given, room temperature depicts a temperature in therange 20-25° C. Percentages are by weight of the polymer substrateunless otherwise indicated.

Test Methods

NFPA 701 Standard Methods of Fire Tests for Flame-Resistant Textiles andFilms, 1989 and 1996 editions;

UL 94 Test for Flammability of Plastic Materials for Parts in Devicesand Appliances, 5th Edition, Oct. 29, 1996;

Limiting Oxygen Index (LOI), ASTM D-2863;

Cone Calorimetry, ASTM E-1 or ASTM E 1354;

ASTM D 2633-82, burn test.

Compound Preparation Examples

EXAMPLE P1 Preparation of Compound 126

A mixture of 25 g4-hydroxy-2,2,6,6-tetramethylpiperidine-1-cyclohexyloxy (0.098 mol), 40mL triethylamine (0.29 mol), and 0.5 g dimethylaminopyridine in 80 mLmethylene chloride is cooled to 0C under nitrogen flow. A solution of 23mL diphenyl chlorophosphate (0.11 mol) is added dropwise over 30minutes. The mixture is allowed to warm to room temperature and isstirred 17 hours. The mixture is concentrated; a 10% ethyl acetate inheptane solution and a 1 N HCl solution are added. The aqueous layer isseparated and extracted with 10% ethyl acetate in heptane solution. Theorganic layers are washed with 1 N HCl, water, and sat. NaHCO₃ solution,dried over MgSO₄, and concentrated. The oil is purified by columnchromatography using heptane and ethyl acetate solvents on silica gel togive 41.5 g (87% yield) of a pale yellow oil. ¹H NMR δ 7.38-7.29 (m),7.26-7.15 (m), 4.85-4.72 (m), 3.62-3.51 (m), 2.06-1.87 (m), 1.78-1.63(m), 1.56-1.48 (m), 1.28-1.10 (m), 1.17 (s), 1.14 (s). ³¹P NMR δ−11.89.

EXAMPLE P2 Preparation of Compound 012

A mixture of 24.2 g tetrabromophthalic anhydride (0.062 mol) in 75 mLacetic acid and 180 mL toluene is heated to reflux, and a solution of 16g 1-(cyclohexyloxy)-2,2,6,6-tetramethyl-4-piperidinamine (see U.S. Pat.No. 5,204,473) in toluene (40 mL) is added. A Dean-Stark trap isattached to the reaction flask. The mixture is refluxed 11.5 hours. Thereaction is allowed to cool and the solvents are removed in vacuo. Theresidue is recrystallized in acetic acid and toluene to give 36.3 gwhite solid (82% yield.) ¹H NMR δ 4.59 (tt), 3.63 (m), 2.51 (t),2.14-1.06 (m). ¹³C NMR δ 163.8, 137.4, 130.3, 121.2, 81.9, 60.0, 44.9,41.8, 34.3, 34.3, 25.9, 25.0, 20.4.

EXAMPLE P3 Preparation of Compound 137

A mixture of 5 g 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl benzoate(0.018 mol), 9.9 mL t-butyl nitrite (0.083 mol), and 1.8mg copper (II)fluoride (0.018 mmol, 0.1 mol %) in 180 mL pyridine is heated to 65-70Cunder nitrogen. A solution of 13.6 g 2,4-dibromoaniline (0.054 mol) in20 mL pyridine is added slowly over a period of 45 minutes. The mixtureis stirred 15 more minutes at 70° C., and is stirred a further threedays at room temperature. The solvent is removed in vacuo; the residueis purified by column chromatography using heptane and ethyl acetatesolvents on silica gel followed by recrystallization in diethyl etherand heptane to give 5 g white crystals (55% yield.) ¹H NMR δ 8.04(d),7.60 (d), 7.58 (t), 7.46 (t), 7.45 (d), 7.31 (dd), 5.40 (tt), 2.14 (d),1.87 (t), 1.47 (s), 1.07 (s).

EXAMPLE P4 Preparation of Compound 040

A solution of3,9-dichloro-2,4,8,10-tetraoxo-3,9-diphosphaspiro[5.5]undecane (see U.S.Pat. No. 4,070,336) (35 g, 0.13 mmol) and triethylamine (56 mL, 0.40mol) in toluene (200 mL) is cooled to 0C under nitrogen. A solution of4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (60.2 g, 0.24 mol) intoluene (200 mL) is added dropwise. The mixture is stirred 18 hours atroom temperature, and the solvents are evaporated. The residue is takenup in water and CH₂Cl₂. The aqueous layer is separated and extractedseveral times with CH₂Cl₂. The organic layers are dried over MgSO₄ andconcentrated, and the residue is recrystallized with heptane to give64.0 g white solid (78% yield.) To the product is added 350 mL toluene,and trace remaining acid is neutralized using concentrated ammoniumhydroxide. The mixture is cooled to 0C under nitrogen. A 70% solution oft-butylhydroperoxide in water (28 mL, 0.20 mol) is extracted intoheptane; the heptane is dried over MgSO₄, filtered, and added dropwiseto the toluene mixture. The mixture is stirred 18 hours at roomtemperature; the product is isolated by filtration to give 56.9 g whitesolid (84% yield.) ¹H NMR δ 4.74(m), 4.64 (ddd), 4.30 (dd), 4.00-4.70(m), 3.59 (m), 2.00 (b), 1.70 (b), 1.00-2.10 (m). ³¹P NMR δ−7.86.

EXAMPLE P5

The following compounds are prepared:

EXAMPLE P6

A copolymer of

is prepared.

EXAMPLE P7

Compounds of Examples P1, P2, P4-P6, are prepared, replacing thecyclohexyloxy group of the hindered amine with n-propoxy, hydroxy,2-methyl-2hydroxypropoxy and oxyl.

Application Examples

EXAMPLE A1

Fiber grade polypropylene is dry blended with the additives of the tablebelow. Each additive is 1% by weight based on the weight of thepolypropylene. Each of the polypropylene formulations is compounded in atwin screw extruder and the fibers are extruded using a Hills fiberextruder. Compounding is carried out at 425° F. The fiber extrusion iscarried at 475° F. and 525° F. Socks are knitted from the fibers and areevaluated for flame retardant efficacy using the NFPA 701 test.

Fiber ext. Drip Burn temp (° F.) (seconds) Blank 475 >100 Blank 525 >1001% Compound 040 475 2.31 1% Compound 137 525 12.79 1% Compound 126 4750.6

The shorter the drip burn time, the more flame retardant theformulationis. It is seen that the compounds of the present inventionprovide significant flame retardancy to polypropylene fibers.

EXAMPLE A2

Molding grade polypropylene (Profax® 6501; Montell) is dry blended withthe test additives and then melt compounded in a twin screw extruder at220° C. Base stabilization is 500 ppm N,N-di(alkyl)hydroxylamineproduced by the direct oxidation of N,N-di(hydrogenated tallow)amine(Irgastab® FS-042) and 500 ppm calcium stearate. Plaques (125 mil) areprepared by injection molding from the formulations using a BoyInjection Molder at 475° F. (246° C.). The specimens are tested forflame retardancy according to the UL-94 vertical burn testspecifications.

The present additives of Examples P1-P7 provide significant flameretardancy.

EXAMPLE A3

Polyethylene fibers are prepared from fiber grade polyethylene by dryblending with test additives and melt compounding at 400° F. Fibers areextruded from this formulation using a Hills laboratory scale fiberextruder. Socks are knitted from the fibers and are tested for flameretardancy according to NFPA 701 vertical burn method. Polyethylenefibers contain 0.5%, 1% or 2% of an additive of present compounds P1-P7.These formulated fibers are tested for flame retardancy according toNFPA 701.

The fibers containing an additive of Examples P1-P7 of the presentinvention exhibit enhanced flame retardancy.

EXAMPLE A4

Molding grade polypropylene (Profax® 6501; Montell) is dry blended withthe test additives of this invention and then melt compounded in a twinscrew extruder at 200° C. under nitrogen. Base stabilization is 500 ppmN,N-di(alkyl)hydroxylamine produced by the direct oxidation ofN,N-di(hydrogenated tallow)amine (Irgastab® FS-042) and 500 ppm calciumstearate. Plaques (125 mil) are prepared by injection molding from theformulations using a Boy Injection Molder at 475° F. (246° C.). Thespecimens are tested for flame retardancy according to the UL-94vertical burn test specifications.

The plaques are tested for flame retardancy by the UL 94V thick sectiontest. The ratings achievable are V-0 (best rating), V-1, and V-2.Additive levels are reported in weight percent based on the totalcomposition.

The results show that the requirements of the V-0 rating in the UL-94vertical burning test are only met by the composition of presentinvention.

EXAMPLE A5

Foam grade polyethylene is dry blended with test additives and then meltcompounded into pellets. The pelletized fully formulated resin is thenblown into foam.

The polyethylene foam prepared contains an instant additive of ExamplesP1-P7. The formulated foam is tested for flame retardancy according tothe UL-94 burn test method.

The foam containing an additive of present Examples P1-P7 exhibitexcellent flame retardancy.

EXAMPLE A6

Wire & cable grade polyethylene is dry blended with test additives andthen melt compounded into pellets. The pelletized fully formulated resinis then extruded onto wire.

Test specimens are tested for flame retardancy using the ASTM D 2633-82burn test conditions. The formulations containing a compound of thepresent invention of Examples P1-P7 exhibit enhanced flame retardancy.

EXAMPLE A7

Fiber grade polyethylene is dry-blended with test additives of presentExamples P1-P7. Non-woven fabrics are produced from the polymer blendformulations by a spun-bonded or melt-blown process.

The non-woven fabrics made thereby are tested for flame retardancyaccording to the NFPA 701 vertical burn test specifications. The fabricscontaining the present compounds of Examples P1-P7 exhibit excellentflame retardancy.

EXAMPLE A8

Fiber grade polypropylene is dry-blended with test additives of ExamplesP1-P7. Non-woven fabrics are produced from the polymer blendformulations by a spun-bonded or melt-blown process.

The non-woven fabrics made thereby are tested for flame retardancyaccording to the NFPA 701 vertical burn test specifications. The fabricscontaining an additive selected from present Examples P1-P7 exhibitexcellent flame retardancy.

EXAMPLE A9

Molding grade polystyrene is dry-blended with test additives of presentExamples P1-P7 and then melt compounded. Specimens are injection moldedfrom these test formulations.

The specimens are tested for flame retardancy according to the UL-94burn test specifications. The molded specimens containing the presentcompounds of Examples P1-P7 exhibit excellent flame retardancy.

EXAMPLE A10

Foam grade polystyrene is dry-blended with test additives of ExamplesP1-P7 and then melt compounded. Foam polystyrene specimens are preparedfrom these test formulations.

The specimens are tested for flame retardancy according to the UL-94burn test specifications. The foam specimens containing the presentcompounds of Examples P1-P7 exhibit excellent flame retardancy.

EXAMPLE A11

Molding grade ABS is dry blended with the an additive selected frompresent Examples P1-P7, then melt compounded at 425° F. (218° C.).Specimens 125 mil (⅛″) thick are then injection molded from thisformulation using a Boy Injection Molder at 450° F. (232° C.). Thespecimens are tested for flame retardancy according to the UL-94vertical burn test specifications.

The specimens containing the present compounds selected from ExamplesP1-P7 exhibit excellent flame retardancy.

EXAMPLE A12

Fiber grade polypropylene is dry blended with an additive selected fromthe present Examples P1-P7, and then melt compounded at 234° C. (450°F.) into pellets. The pelletized fully formulated resin is then spun at246° C. (475° F.) into fiber using a Hills laboratory model fiberextruder. The spun tow of 41 filaments is stretched at a ratio of 1:3.2to give a final denier of 615/41.

Socks are knitted from the stabilized polypropylene fiber on aLawson-Hemphill Analysis Knitter and tested under NFPA 701 vertical burnprocedure. The time in seconds for the knitted sock to extinguish afterthe insult flame is removed is reported as “After Flame”. Both themaximum time for any one replicate and the total time for ten replicatesare measured. Efficacy as a flame retardant is demonstrated when lowAfter Flame times are observed relative to a blank sample containing noflame retardant.

The specimens containing the present compounds selected from ExamplesP1-P7 exhibit excellent flame retardancy.

EXAMPLE A13

Film grade polyethylene is dry blended with the with an additiveselected from the present Examples P1-P7, and then melt compounded intopellets. The pelletized fully formulated resin is then blown at 205° C.using a MPM Superior Blown film extruder.

The films are tested for flame retardancy under NFPA 701 testconditions. The specimens containing the present compounds selected fromExamples P1-P7 exhibit excellent flame retardancy.

Film grade polypropylene is handled in a similar fashion andpolypropylene films containing the instant compounds also show flameretardancy.

EXAMPLE A14

Molded test specimens are prepared by injection molding thermoplasticolefin (TPO) pellets containing a present test compound selected fromcompounds of Examples P1-P7. The TPO formulations may also contain apigment, a phosphite, a phenolic antioxidant or hydroxylamine, a metalstearate, a UV absorber or a hindered amine stabilizer or a mixture ofhindered amine and UV absorber.

Pigmented TPO formulation composed of polypropylene blended with arubber modifier where the rubber modifier is an in-situ reactedcopolymer or blended product containing copolymers of propylene andethylene with or without a ternary component such as ethylidenenorbornene are stabilized with a base stabilization system consisting ofan N,N-dialkylhydroxylamine or a mixture of hindered phenolicantioxidant and an organophosphorus compound.

The TPO plaques are tested for flame retardancy using the UL-94 VerticalBurn conditions. A minimum of three replicates are tested. Efficacy as aflame retardant is measured relative to a blank sample containing noflame retardant.

The specimens containing the present compounds of Examples P1-P7 exhibitexcellent flame retardancy.

EXAMPLE A15

Film grade ethylene/vinyl acetate (EVA) copolymers containing 20 weightpercent or less of vinyl acetate are dry blended with test additives andthen melt compounded into pellets. The pelletized fully formulated resinis then blown into a film at 205° C. using a MPM Superior Blown-filmextruder.

The films are tested for flame retardancy under NFPA 701 testconditions. The films containing the present compounds selected fromExamples P1-P7 exhibit excellent flame retardancy.

Film grade low density polyethylene (LDPE) which contains some linearlow density polyethylene (LLDPE) and/or ethylene/vinyl acetate (EVA) aredry blended with test additives and blown into film as described abovefor EVA copolymer resin. The films are tested for flame retardancy underNFPA 701 test conditions and those containing the present compoundsselected from Examples P1-P7 exhibit excellent flame retardancy.

EXAMPLE A16

High impact polystyrene (HIPS) polymer (STYRON® 484C, Dow Chemical Co.)is compounded with a present compound of Examples P1-P7, pelletized andthen injection or compression molded into plaques. These plaques aretested for flame retardant efficacy using cone calorimetry, LOI or UL-94test method.

The plaques containing an instant compound of Examples P1-P7, exhibitexcellent flame retardancy. Flame retardant HIPS polymers findapplication in housings for business machines.

EXAMPLE A17

This Example shows the efficacy of the present compounds in PVCformulations. Such formulations are useful in flexible or rigid PVC andin wire and cable applications.

Typical formulations are seen below:

Component parts parts parts parts PVC resin 100 100 100 100 tinmercaptide 1.5 — 2.0 — tin carboxyate — 2.5 — 2.0 process aid 1.5 1.52.0 2.0 impact mod. 6.0 6.0 7.0 7.0 paraffin wax 1.0 0.3 1.0 1.0polyethyl wax 0.1 0.1 0.2 0.2 Ca stearate 1.0 — 0.8 — pigment 1.0 0.95.0 5.0

Fully formulated PVC containing one of the present compounds of ExamplesP1-P7 is pelletized and then injection molded into test plaques forexamination of flame retardancy using the UL-94 or LOI test method.

The PVC plaques containing the instant compounds of Examples P1-P7demonstrate excellent flame retardancy.

EXAMPLE A18

Fiber grade poly(ethylene terephthalate) (PET) is dry blended with atest additive of Examples P1-P7, then melt compounded at 550° F. andthen pelletized. The polyester pellets are dried at 175° F. for 24 hoursunder vacuum. The dried pellets are extruded into fibers using a Hillslaboratory scale fiber extruder at 550° F. Socks are knitted from thesefibers and tested for flame retardancy according to NFPA 701 testmethod.

The fibers containing a present compound of Examples P1-P7, exhibitenhanced flame retardancy.

EXAMPLE A19

Thermoplastic resins including polypropylene, polyethylene homopolymer,polyolefin copolymer or thermoplastic olefins (TPO), high impactpolystyrene (HIPS) and ABS are dry blended with an instant compound ofExamples P1-P7, and then melt compounded into pellets. The pelletizedfully formulated resin is then processed into a useful article such asextrusion into fiber; blown or cast extrusion into film; blow moldedinto bottles; injection molded into molded articles, thermoformed intomolded articles, extruded into wire and cable housing or rotation moldedinto hollow articles.

The articles containing the instant compounds of Examples P1-P7 exhibitflame retardancy when tested by a known standard test method.

Polyethylene wire and cable applications are tested for flame retardancyaccording to ASTM D-2633-82 burn test method. The materials containingthe instant compounds of Examples P1-P7 show excellent flame retardancy.

EXAMPLE A20

Articles prepared according to Example A19 which additionally contain anorganophosphorus stabilizer selected from the group consisting oftris(2,4-di-tert-butylphenyl) phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,2,2′,2“-nitrilo[triethyl-tris-(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], tetrakis(2,4-di-butylphenyl) 4,4′-biphenylenediphonite,tris(nonylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythrityl diphosphite, 2,2′-ethylidenebis(2,4-di-tert-butylphenyl)fluorophosphite and 2-butyl-2-ethylpropan-1,3-diyl2,4,6-tri-tert-butylphenyl phosphite exhibit good flame retardancyproperties.

EXAMPLE A21

Articles prepared according to Example A19 which additionally contain ao-hydroxyphenyl-2H-benzotriazole, a hydroxyphenyl benzophenone or ao-hydroxyphenyl-s-triazine UV absorber selected from the groupconsisting of 2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,2,4-di-tert-butylphenyl 3,5-di-tert-butyl4-hydroxybenzoate,2-hydroxy-4-n-octyloxybenzophenone and2,4-bis(2,4-dimethyphenyl)-6-(2-hydroxy-4-octyloxy-phenyl)-s-triazineexhibit good flame retardancy.

EXAMPLE A22

Articles prepared according to Example A19 which additionally contain ao-hydroxyphenyl-2H-benzotriazole, a hydroxyphenyl benzophenone or ao-hydroxyphenyl-s-triazine UV absorber selected from the groupconsisting of 2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole,2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole,2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,2,4-di-tert-butylphenyl 3,5-di-tert-butyl4-hydroxybenzoate,2-hydroxy-4-n-octyloxybenzophenone and2,4-bis(2,4-dimethyphenyl)-6-(2-hydroxy-4-octyloxy-phenyl)-s-triazineexhibit good flame retardancy properties.

EXAMPLE A23

Examples A1-A22 are repeated with the co-use of a traditionalhalogenated flame retardant. The halogenated flame retardant is selectedfrom

-   -   decabromodiphenyl oxide (DBDPO; SAYTEX® 102E),    -   tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate (PB 370®, FMC        Corp.),    -   bis(2,3-dibromopropyl ether) of bisphenol A (PE68),    -   ethylene-bis(tetrabromophthalimide) (SAYTEX® BT-93),    -   1,2-bis(tribromophenoxy)ethane (FF680),    -   tetrabromo-bisphenol A (SAYTEX® RB100),    -   ethylene bis-(dibromo-norbornanedicacboximide) (SAYTEX® BN-451),        or    -   tris-(2,3-dibromopropyl)-isocyanurate.

Excellent results are achieved.

1. A compound of formula I

where R is hydrogen or methyl, G₁ and G₂ are independently alkyl of 1 to4 carbon atoms or are together pentamethylene, x, y and z are eachindependently greater than or equal to 1, L is independently of eachother a direct bond or a hydrocarbylene group, Z₁ is hydrogen orhydrocarbyl or —OR₁, —OCOR₁, —COOR₁, —CONR₁R₂, —NR₁COR₂, —COR₁ or—NR₁R₂, R₁ and R₂ are independently of each other hydrogen orhydrocarbyl, or R₁ and R₂ together form a hydrocarbylene group, E isoxyl, hydroxyl, alkoxy, cycloalkoxy, aralkoxy, aryloxy, —O—CO—OG,—O—Si(G)₃, or —O—CH₂-OG where G is selected from the group consisting ofhydrogen, an aliphatic, araliphatic and aromatic moiety; or E is—O—T—(OH)_(b), T is a straight or branched chain alkylene of ito 18carbon atoms, cycloalkylene of 5 to 18 carbon atoms, cycloalkenylene of5 to 18 carbon atoms, a straight or branched chain alkylene of 1 to 4carbon atoms substituted by phenyl or by phenyl substituted by one ortwo alkyl groups of 1 to 4 carbon atoms, b is 1, 2 or 3 with the provisothat b cannot exceed the number of carbon atoms in T, and when b is 2 or3, each hydroxyl group is attached to a different carbon atoms of T, andFRM is independently of each other flame retardant moiety

where X is chlorine or bromine.
 2. A compound according to claim 1 inwhich E is oxyl, hydroxyl, methoxy, propoxy, cyclohexyloxy or octyloxy.3. A compound according to claim 1 in which L is a direct bond.
 4. Acompound according to claim 1 that comprises a sterically hinderedhydrocarbyloxyamine moiety selected from the group consisting of


5. A compound according to claim 1 of formula